U.S. patent number 4,568,663 [Application Number 06/626,022] was granted by the patent office on 1986-02-04 for cobalt catalysts for the conversion of methanol to hydrocarbons and for fischer-tropsch synthesis.
This patent grant is currently assigned to Exxon Research and Engineering Co.. Invention is credited to Charles H. Mauldin.
United States Patent |
4,568,663 |
Mauldin |
February 4, 1986 |
Cobalt catalysts for the conversion of methanol to hydrocarbons and
for Fischer-Tropsch synthesis
Abstract
A rhenium promoted cobalt catalyst, especially a rhenium and
thoria promoted cobalt catalyst, and process for the conversion of
methanol to hydrocarbons. Methanol is contacted, preferably with
added hydrogen, over said catalyst, or synthesis gas is contacted
over said catalyst to produce, at reaction conditions, an admixture
of C.sub.10 + linear paraffins and olefins. These hydrocarbons can
be further refined to high quality middle distillate fuels, and
other valuable products such as mogas, diesel fuel, jet fuel, lubes
and speciality solvents, particularly premium middle distillate
fuels of carbon number ranging from about C.sub.10 to about
C.sub.20.
Inventors: |
Mauldin; Charles H. (Baton
Rouge, LA) |
Assignee: |
Exxon Research and Engineering
Co. (Florham Park, NJ)
|
Family
ID: |
36848403 |
Appl.
No.: |
06/626,022 |
Filed: |
June 29, 1984 |
Current U.S.
Class: |
502/325; 518/715;
585/733 |
Current CPC
Class: |
B01J
23/75 (20130101); B01J 23/8896 (20130101); C07C
1/0435 (20130101); C07C 1/20 (20130101); C10G
3/45 (20130101); C10G 3/48 (20130101); B01J
23/83 (20130101); Y02P 20/52 (20151101); C07C
2521/06 (20130101); C07C 2523/10 (20130101); C07C
2523/12 (20130101); C07C 2523/36 (20130101); C07C
2523/75 (20130101); C07C 2523/83 (20130101); C07C
2523/889 (20130101); C10G 2300/1022 (20130101); Y02P
30/20 (20151101) |
Current International
Class: |
B01J
23/889 (20060101); B01J 23/76 (20060101); C07C
1/20 (20060101); C07C 1/04 (20060101); C07C
1/00 (20060101); C10G 3/00 (20060101); B01J
021/06 (); B01J 023/12 (); B01J 023/36 (); B01J
023/74 () |
Field of
Search: |
;502/300,325,332,350
;518/715 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2073237 |
|
Mar 1981 |
|
GB |
|
610558 |
|
Nov 1978 |
|
SU |
|
Other References
Chemical Abstracts, vol. 96, p. 170, Item 183828a (1982). .
92:129385h; The Synthesis of Solid Hydrocarbons from Methanol;
Shima, Kensuke, Morita, Tauyoshi (Miyazaki Univ., Miyazaki, Japan);
Nouveau Journal DeChime, vol. 6, No. 10-1982, p. 459. .
Fischer-Tropsch Synthesis of Hydrocarbons Over Ruthenium Supported
on Transition Metal Oxides; Kikuchi, Nomura, Matsumoto and Morita
(Waseda University, Tokyo 160); Pan-Pacific Synfuels Conference,
vol. I, Nov. 17-19, 1982 Tokyo, pp. 1-10. .
Fischer-Tropsch Synthesis Over Titania-Supported Ruthenium
Catalysts; Kikuchi, Matsumoto, Takahashi, Machino and Morita
(Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo, Japan); Printed
in the Netherlands; Applied Catalysis, 10 (1984), pp.
251-260..
|
Primary Examiner: Shine; W. J.
Attorney, Agent or Firm: Proctor; Llewellyn A.
Claims
What is claimed is:
1. A catalyst useful for the conversion at reaction conditions of
methanol or synthesis gas to hydrocarbons by contact with a
catalyst which comprises cobalt and thoria in catalytically active
amounts, and rhenium, composited with an inorganic oxide support in
weight ratio of rhenium:cobalt ranging from about 0.025:1 to about
0.10:1.
2. The composition of claim 1 wherein the catalyst contains from
about 2 percent to about 25 percent cobalt, based on the weight of
the catalyst composition.
3. The composition of claim 2 wherein the catalyst contains from
about 5 to about 15 percent cobalt, based on the weight of the
catalyst composition.
4. A catalyst useful for the conversion at reaction conditions of
methanol or synthesis gas to hydrocarbons by contact with a
catalyst which comprises rhenium, cobalt, and thoria in
catalytically active amounts composited with an inorganic oxide
support, the catalyst containing from about 2 percent to about 25
percent cobalt, and from about 0.1 percent to about 10 percent
thoria, based on the total weight of the catalyst, the weight ratio
of rhenium:cobalt ranging from about 0.025:1 to about 0.10:1, and
the ratio of cobalt:thoria ranging from about 20:1 to about
1:1.
5. The composition of claim 4 wherein the catalyst comprises from
about 5 percent to about 15 percent cobalt, and from about 0.5
percent to about 5 percent thoria.
6. The composition of claim 4 wherein the inorganic oxide support
is titania or a titania-containing support.
7. The composition of claim 6 wherein the rutile:anatase content of
the titania is at least about 2:3.
8. A catalyst useful for the conversion at reaction conditions of
methanol or synthesis gas to hydrocarbons by contact with a
catalyst which comprises from about 2 percent to about 25 percent
cobalt, and rhenium, composited with titania or a
titania-containing support, the weight ratio of rhenium:cobalt
ranging from about 0.025:1 to about 0.10:1.
9. The composition of claim 8 wherein the catalyst comprises
rhenium, cobalt, and thoria dispersed on the support, the catalyst
containing from about 0.1 percent to about 10 percent thoria, based
on the total weight of the catalyst.
10. The composition of claim 8 wherein the rutile:anatase content
of the titania is at least about 2:3.
11. The composition of claim 8 wherein the rutile:antase content of
the titania ranges from about 3:2 to about 100:1, or higher.
12. The composition of claim 9 wherein the ratio of cobalt:thoria
ranges from about 20:1 to about 1:1.
13. The composition of claim 9 wherein the weight ratio of
cobalt:thoria ranges from about 15:1 to about 2:1.
14. The composition of claim 9 wherein the catalyst contains from
about 5 to about 15 percent cobalt, based on the weight of the
catalyst composition.
15. A catalyst useful for the conversion at reaction conditions of
methanol or synthesis gas to hydrocarbons by contact with a
catalyst which comprises from about 2 percent to about 25 percent
cobalt, from about 0.1 percent to about 10 percent thoria, based on
the total weight of the catalyst, and rhenium, composited with
titania or a titania-containing support, the weight ratio of
rhenium:cobalt ranging from about 0.025:1 to about 0.10:1, and the
rutile:anatase content of the titania is at least about 2:3.
16. The composition of claim 15 wherein the rutile:anatase content
of the titania ranges from about 3:2 to about 100:1, or
greater.
17. The composition of claim 15 wherein the ratio of cobalt:thoria
ranges from about 20:1 to about 1:1.
18. The composition of claim 15 wherein the weight ratio of
cobalt:thoria ranges from about 15:1 to about 2:1.
19. The composition of claim 15 wherein the catalyst contains from
about 5 to about 15 percent cobalt, based on the weight of the
catalyst composition.
20. A catalyst useful for the conversion at reaction conditions of
methanol or synthesis gas to hydrocarbons by contact with a
catalyst which comprises a catalytically active amount of cobalt,
and rhenium, composited with titania or a titania-containing
support, the weight ratio of rhenium:cobalt ranging from about
0.025:1 to about 0.10:1.
Description
BACKGROUND OF THE INVENTION
I. Field of the Invention
This invention relates to improvements in a process for the
conversion of methanol to hydrocarbons, to improvements in a
Fischer-Tropsch process, and to improvements in Fischer-Tropsch
catalysts. In particular, it relates to improved cobalt catalysts,
and process for using such catalysts in the conversion of methanol,
and Fischer-Tropsch synthesis to produce hydrocarbons, especially
C.sub.10 + distillate fuels, and other valuable products.
II. The Prior Art
Methane is often available in large quantities from process streams
either as an undesirable by-product in admixture with other gases,
or as an off gas component of a process unit, or units. More
importantly, however, methane is the principle component of natural
gas, and it is produced in considerable quantities in oil and gas
fields. The existence of large methane, natural gas reserves
coupled with the need to produce premium grade transportation
fuels, particularly middle distillate fuels, creates a large
incentive for the development of a new gas-to-liquids process.
Conventional technology, however, is not entirely adequate for such
purpose. Nonetheless, technology is available for the conversion of
natural gas, to produce methanol, a product of currently limited
market ability. However, to utilize the existing technology, there
is a need for a process suitable for the conversion of methanol to
high quality transportation fuels, particularly middle distillate
fuels. On the other hand, the technology to convert natural gas, or
methane, to synthesis gas is well established, and the conversion
of the synthesis gas to hydrocarbons can be carried out via
Fischer-Tropsch synthesis.
Fischer-Tropsch synthesis for the production of hydrocarbons from
carbon monoxide and hydrogen is now well known in the technical and
patent literature. The first commercial Fischer-Tropsch operation
utilized a cobalt catalyst, though later more active iron catalysts
were also commercialized. An important advance in Fischer-Tropsch
catalysts occurred with the use of nickel-thoria on kieselguhr in
the early thirties. This catalyst was followed within a year by the
corresponding cobalt catalyst, 100Co:18ThO.sub.2 :100 kieselguhr,
parts by weight, and over the next few years by catalysts
constituted to 100Co:18ThO.sub.2 :200 kieselguhr and
100Co:5ThO.sub.2 :8MgO:200 kieselguhr, respectively. The Group VIII
non-noble metals, iron, cobalt, and nickel have been widely used in
Fischer-Tropsch reactions, and these metals have been promoted with
various other metals, and supported in various ways on various
substrates. Most commercial experience has been based on cobalt and
iron catalysts. The cobalt catalysts, however, are of generally low
activity necessitating a multiple staged process, as well as low
synthesis gas throughput. The iron catalysts, on the other hand,
are not really suitable for natural gas conversion due to the high
degree of water gas shift activity possessed by iron catalysts.
Thus, more of the synthesis gas is converted to carbon dioxide in
accordance with the equation: H.sub.2 +2CO.fwdarw.(CH.sub.2).sub.x
+CO.sub.2 ; with too little of the synthesis gas being converted to
hydrocarbons and water as in the more desirable reaction,
represented by the equation: 2H.sub.2 +CO.fwdarw.(CH.sub.2).sub.x
+H.sub.2 O.
There exists a need in the art for a process useful for the
conversion of methanol and synthesis gas at high conversion levels,
and at high yields to premium grade transportation fuels,
especially C.sub.10 + distillate fuels; particularly without the
production of excessive amounts of carbon dioxide.
III. Objects
It is, accordingly, a primary objective of the present invention to
supply these needs.
A particular object is to provide novel catalysts, and process for
the conversion of methanol and synthesis gas, i.e., carbon monoxide
and hydrogen, respectively, to high quality distillate fuels
characterized generally as admixtures of C.sub.10 + linear
paraffins and olefins.
A further and more specific object is to provide new and improved
supported cobalt catalysts, notably cobalt-titania and
cobalt-thoria-titania catalysts, which in methanol conversion
reactions, and in Fischer-Tropsch synthesis and subsequent catalyst
regeneration, are highly active, and exhibit high stability.
A yet further object is to provide a process which utilizes such
catalysts for the preparation of hydrocarbons, notably high quality
middle distillate fuels characterized generally as admixtures of
linear paraffins and olefins, from methanol, or from a feed mixture
of carbon monoxide and hydrogen via the use of such catalysts.
IV. The Invention
These objects and others are achieved in accordance with the
present invention which, in general, embodies:
(A) A particulate catalyst composition constituted of a
catalytically active amount of cobalt, or cobalt and thoria, to
which is added sufficient rhenium to obtain, at corresponding
process conditions, improved activity and stability in production
of hydrocarbons from methanol, or in the production of hydrocarbons
via carbon monoxide-hydrogen synthesis reactions than a catalyst
composition otherwise similar except that it does not contain
rhenium. Suitably, rhenium is added to the cobalt catalyst, or
cobalt and thoria catalyst, in amount sufficient to form a catalyst
having a rhenium:cobalt in weight ratio greater than about 0.010:1,
preferably from about 0.025:1 to about 0.10:1. In terms of absolute
concentrations, from about 0.05 percent to about 3 percent of
rhenium, preferably from about 0.15 percent to about 1 percent of
rhenium, based on the total weight of the catalyst composition (dry
basis), is dispersed with the catalytically active amount of cobalt
upon an inorganic oxide support, preferably upon titania
(TiO.sub.2), or a titania-containing support, particularly titania
wherein the rutile:anatase weight ratio is at least about 2:3. This
ratio is determined in accordance with ASTM D 3720-78: Standard
Test Method for Ratio of Anatase to Rutile in Titanium Dioxide
Pigments By Use of X-Ray Diffraction. Suitably, in terms of
absolute concentrations the cobalt is present in the composition in
amounts ranging from about 2 percent to about 25 percent,
preferably from about 5 percent to about 15 percent, based on the
total weight of the catalyst composition (dry basis), and
sufficient rhenium is added to form a catalyst having a weight
ratio of rhenium:cobalt greater than about 0.010:1, preferably from
about 0.025:1 to about 0.10:1, based on the total weight of the
cobalt and rhenium contained in the catalyst composition (dry
basis). The absolute concentration of each metal is, of course,
preselected to provide the desired ratio of rhenium:cobalt, as
heretofore expressed. Thoria can also be added to the composition,
and is preferably added to the catalyst when it is to be used in
the conversion of methanol. The thoria is dispersed on the support
in amounts ranging from about 0.1 percent to about 10 percent,
preferably from about 0.5 percent to about 5 percent, based on the
total weight of the catalyst composition (dry basis). Suitably, the
thoria promoted cobalt catalyst contains Co and ThO.sub.2 in ratio
of Co:ThO.sub.2 ranging from about 20:1 to about 1:1, preferably
from about 15:1 to about 2:1, based on the weight of the total
amount of Co and ThO.sub.2 contained on the catalyst. These
catalyst compositions, it has been found, produce a product which
is predominately C.sub.10 + linear paraffins and olefins, with very
little oxygenates. These catalysts provide high selectivity, high
activity, and activity maintenance in methanol conversion, or in
the conversion of the carbon monoxide and hydrogen to distillate
fuels. These catalysts are also highly stable, particularly during
high temperature air regenerations which further extend catalyst
life.
(B) A process wherein the particulate catalyst composition of (A),
supra, is formed into a bed, and the bed of catalyst contacted at
reaction conditions with a methanol feed, or feed comprised of an
admixture of carbon monoxide and hydrogen, or compound decomposable
in situ within the bed to generate carbon monoxide and hydrogen, to
produce a product of middle distillate fuel quality constituted
predominately of linear paraffins and olefins, particularly
C.sub.10 + linear paraffins and olefins.
(i) In conducting the methanol reaction the partial pressure of
methanol within the reaction mixture is generally maintained above
about 100 pounds per square inch absolute (psia), and preferably
above about 200 psia. It is preferable to add hydrogen with the
methanol. Suitably methanol, and hydrogen, are employed in molar
ratio of CH.sub.3 OH:H.sub.2 above about 4:1, and preferably above
8:1, to increase the concentration of C.sub.10 + hydrocarbons in
the product. Suitably, the CH.sub.3 OH:H.sub.2 molar ratio, where
hydrogen is employed, ranges from about 4:1 to about 60:1, and
preferably the methanol and hydrogen are employed in molar ratio
ranging from about 8:1 to about 30:1. Inlet hydrogen partial
pressures preferably range below about 80 psia, and more preferably
below about 40 psia; inlet hydrogen partial pressures preferably
ranging from about 5 psia to about 80 psia, and more preferably
from about 10 psia to about 40 psia. In general, the reaction is
carried out at liquid hourly space velocities ranging from about
0.1 hr.sup.-1 to about 10 hr.sup.-1, preferably from about 0.2
hr.sup.-1 to about 2 hr.sup.-1, and at temperatures ranging from
about 150.degree. C. to about 350.degree. C., preferably from about
180.degree. C. to about 250.degree. C. Methanol partial pressures
preferably range from about 100 psia to about 1000 psia, more
preferably from about 200 psia to about 700 psia.
(ii) In general, the synthesis reaction is carried out at an
H.sub.2 :CO mole ratio of greater than about 0.5, and preferably
the H.sub.2 :CO mole ratio ranges from about 0.1 to about 10, more
preferably from about 0.5 to about 4, at gas hourly space
velocities ranging from about 100 V/Hr/V to about 5000 V/Hr/V,
preferably from about 300 V/Hr/V to about 1500 V/Hr/V, at
temperatures ranging from about 160.degree. C. to about 290.degree.
C., preferably from about 190.degree. C. to about 260.degree. C.,
and pressures above about 80 psig, preferably ranging from about 80
psig to about 600 psig, more preferably from about 140 psig to
about 400 psig. In its most preferred form, a bed of catalyst
comprised of from about 5 percent to about 15 percent cobalt,
containing sufficient rhenium to provide a catalyst containing
rhenium:cobalt in ratio ranging from about 0.025:1 to about 0.10:1,
is dispersed on titania, preferably a high purity titania, and a
bed of such catalyst is contacted with a gaseous admixture of
carbon monoxide and hydrogen, or compound decomposable in situ
within the bed to generate carbon monoxide and hydrogen.
The product of either the methanol conversion reaction, or
synthesis reaction generally and preferably contains 60 percent,
more preferably 75 percent or greater, C.sub.10 + liquid
hydrocarbons which boil above 160.degree. C. (320.degree. F.).
It is found that cobalt and rhenium, or cobalt, thoria and rhenium,
supported on titania, or other titania-containing support provides
a catalyst system which exhibits superior methanol conversion, or
hydrocarbon synthesis characteristics in Fischer-Tropsch reactions.
The titania-containing supports used in the practice of this
invention are preferably oxides having surface areas of from about
1 to about 120 m.sup.2 g.sup.-1, preferably from about 10 to about
60 m.sup.2 g.sup.-1.
Rhenium-cobalt/titania and rhenium-thoria-cobalt/titania catalysts
exhibit high selectively in the conversion of methanol to
hydrocarbon liquids, or synthesis of hydrocarbon liquids from
carbon monoxide and hydrogen. The catalysts employed in the
practice of this invention may be prepared by techniques known in
the art for the preparation of other catalysts. The catalyst can,
e.g., be prepared by gellation, or cogellation techniques. Suitably
however the metals can be deposited on a previously pilled,
pelleted, beaded, extruded, or sieved support material by the
impregnation method. In preparing catalysts, the metals are
deposited from solution on the support in preselected amounts to
provide the desired absolute amounts, and weight ratio of the
respective metals, or cobalt, rhenium, and thoria. Suitably, the
cobalt and rhenium are composited with the support by contacting
the support with a solution of a cobalt-containing compound, or
salt, or a rhenium-containing compound, or salt, e.g., a nitrate,
carbonate or the like. The thoria, where thoria is to be added, can
then be composited with the support as a thorium compound or salt
in similar manner, or the thorium can first be impregnated upon the
support, followed by impregnation of the cobalt, or rhenium, or
both. Optionally, the thorium and cobalt, or thoria, cobalt, and
rhenium can be co-impregnated upon the support. The cobalt, rhenium
and thorium compounds used in the impregnation can be any
organometallic or inorganic compounds which decompose to give
cobalt, rhenium, and thorium oxides upon calcination, such as a
cobalt, rhenium, or thorium nitrate, acetate, acetylacetonate,
naphthenate, carbonyl, or the like. The amount of impregnation
solution used should be sufficient to completely immerse the
carrier, usually within the range from about 1 to 20 times of the
carrier by volume, depending on the metal, or metals, concentration
in the impregnation solution. The impregnation treatment can be
carried out under a wide range of conditions including ambient or
elevated temperatures. Metal components other than rhenium and
cobalt (or rhenium, cobalt and thorium) can also be added. The
introduction of an additional metal, or metals, into the catalyst
can be carried out by any method and at any time of the catalyst
preparation, for example, prior to, following or simultaneously
with the impregnation of the support with the cobalt and rhenium
components. In the usual operation, the additional component is
introduced simultaneously with the incorporation of the cobalt and
rhenium, or cobalt, rhenium, and thorium components.
Titania is used as a support, or in combination with other
materials for forming a support. The titania used for the support
in either methanol or syngas conversions, however, is preferably
one where the rutile:anatase ratio is at least about 2:3 as
determined by x-ray diffraction (ASTM D 3720-78). Preferably, the
titania used for the catalyst support of catalysts used in syngas
conversion is one wherein the rutile:anatase ratio is at least
about 3:2. Suitably the titania used for syngas conversions is one
containing a rutile:anatase ratio of from about 3:2 to about 100:1,
or higher, preferably from about 4:1 to about 100:1, or higher. A
preferred, and more selective catalyst for use in methanol
conversion reactions is one containing titania wherein the
rutile:anatase ranges from about 2:3 to about 3:2. The surface area
of such forms of titania are less than about 50 m.sup.2 /g. This
weight of rutile provides generally optimum activity, and C.sub.10
+ hydrocarbon selectivity without significant gas and CO.sub.2
make.
The catalyst, after impregnation, is dried by heating at a
temperature above about 30.degree. C., preferably between
30.degree. C. and 125.degree. C., in the presence of nitrogen or
oxygen, or both, or air, in a gas stream or under vacuum. It is
necessary to activate the cobalt-titania, or thoria promoted
cobalt-titania catalyst prior to use. Preferably, the catalyst is
contacted with oxygen, air, or other oxygen-containing gas at
temperature sufficient to oxidize the cobalt, and convert the
cobalt to Co.sub.3 O.sub.4. Temperatures ranging above about
150.degree. C., and preferably above about 200.degree. C. are
satisfactory to convert the cobalt to the oxide, but temperatures
up to about 500.degree. C. such as might be used in the
regeneration of a severely deactivated catalyst, can generally be
tolerated. Suitably, the oxidation of the cobalt is achieved at
temperatures ranging from about 150.degree. C. to about 300.degree.
C. The cobalt, or cobalt and rhenium metals contained on the
catalyst are then reduced. Reduction is performed by contact of the
catalyst, whether or not previously oxidized, with a reducing gas,
suitably with hydrogen or a hydrogen-containing gas stream at
temperatures, above about 250.degree. C.; preferably above about
300.degree. C. Suitably, the catalyst is reduced at temperatures
ranging from about b 250.degree. C. to about 500.degree. C., and
preferably from about 300.degree. C. to about 450.degree. C., for
periods ranging from about 0.5 to about 24 hours at pressures
ranging from ambient to about 40 atmospheres. Hydrogen, or a gas
containing hydrogen and inert components in admixture is
satisfactory for use in carrying out the reduction.
If it is necessary to remove coke from the catalyst, the catalyst
can be contacted with a dilute oxygen-containing gas and the coke
burned from the catalyst at controlled temperature below the
sintering temperature of the catalyst. The temperature of the burn
is controlled by controlling the oxygen concentration and inlet gas
temperature, this taking into consideration the amount of coke to
be removed and the time desired to complete the burn. Generally,
the catalyst is treated with a gas having an oxygen partial
pressure of at least about 0.1 psi, and preferably in the range of
from about 0.3 psi to about 2.0 psi to provide a temperature
ranging from about 300.degree. C. to about 550.degree. C., at
static or dynamic conditions, preferably the latter, for a time
sufficient to remove the coke deposits. Coke burn-off can be
accomplished by first introducing only enough oxygen to initiate
the burn while maintaining a temperature on the low side of this
range, and gradually increasing the temperature as the flame front
is advanced by additional oxygen injection until the temperature
has reached optimum. Most of the coke can be readily removed in
this way. The catalyst is then reactivated, reduced, and made ready
for use by treatment with hydrogen or hydrogen containing gas as
with a fresh catalyst.
The invention will be more fully understood by reference to the
following demonstrations and examples which present comparative
data illustrating its more salient features. All parts are given in
terms of weight except as otherwise specified. Feed compositions
are expressed as molar ratios of the components.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 5 graphically depict data presented in the following
examples.
The "Schulz-Flory Alpha" is a known method for describing the
product distribution in Fischer-Tropsch synthesis reactions. The
Schulz-Flory Alpha is the ratio of the rate of chain propagation to
the rate of propagation plus termination, and is described from the
plot of ln (Wn/n) versus n, where Wn is the weight fraction of
product with a carbon number of n. In the examples below, an Alpha
value was derived from the C.sub.10 /C.sub.20 portion of the
product. The Alpha value is thus indicative of the selectively of
the catalyst for producing heavy hydrocarbons from the synthesis
gas, and is indicative of the approximate amount of C.sub.10 +
hydrocarbons in the product. For example, a Schulz-Flory Alpha of
0.80 corresponds to about 35% by weight of C.sub.10 + hydrocarbons
in the product, a generally acceptable level of C.sub.10 +
hydrocarbons. A Schulz-Flory Alpha of 0.85, a preferred Alpha
value, corresponds to about 54% by weight of C.sub.10 +
hydrocarbons in the products, and a Schulz-Flory Alpha of 0.90, a
more preferred Alpha value, corresponds to about 74% by weight of
C.sub.10 + hydrocarbons in the product.
The following data show that the addition of a small amount of
rhenium to a Co--TiO.sub.2 catalyst maintains the cobalt in a high
state of dispersion and stabilizes the catalyst during high
temperature air treatment. The rhenium thus maintains the very high
activity of the catalyst which is characteristic of one having
well-dispersed cobalt on the TiO.sub.2. The high activity of
Co--Re--TiO.sub.2 permits high conversion operations at low
temperature where excellent selectivity is obtained in the
conversion of syngas to C.sub.10 + hydrocarbons.
EXAMPLE 1
Titania (Degussa P-25 TiO.sub.2) was used as the support for all of
the catalysts after mixing with sterotex, and after pilling,
grinding, and screening to either 60-150 mesh or 16-20 mesh
(Tyler). Two versions of TiO.sub.2 were prepared by calcining
portions of the TiO.sub.2 in air at 500.degree. C. and 600.degree.
C., respectively, overnight. This gave TiO.sub.2 supports with the
following properties:
______________________________________ Surface Calcination
Rutile:Anatase Area Pore Volume Temperature, .degree.C. Weight
Ratio.sup.(1) m.sup.2 /g ml/g
______________________________________ 500 1.2:1-1:1 33-36
0.28-0.40 600 >30:1 10-16 0.11-0.15
______________________________________ .sup.(1) ASTM D 372078.
Catalysts, of 16-20 mesh size, were prepared from selected portions
of these materials by simple impregnation of the support with
cobaltous nitrate or perrhenic acid, or both, from acetone solution
using a rotary evaporator, drying in a vacuum oven at 150.degree.
C., and calcining of the catalysts for three hours in flowing air
in a quartz tube. The catalysts, identified in the second column of
Table I, were charged to a reactor, reduced in H.sub.2 at
450.degree. C. for one hour, and then reacted with syngas at
200.degree. C., 280 psig, GHSV=1000, and H.sub.2 :CO=2.15 for at
least 16 hours. The performance of each catalyst was monitored by
conventional GC analysis using neon as an internal standard (4% in
the feed). Screening results for these catalysts and dynamic
O.sub.2 chemisorption data are given in Table I. Reference is also
made to FIG. 1 which graphically depicts the data obtained with
most of these catalysts, the percent CO conversion being plotted
against the percent rutile contained in the TiO.sub.2 support, the
rutile:anatase ratio being expressed in both Table I and FIG. 1 as
percent rutile to facilitate construction of the graph.
TABLE I ______________________________________ 280.degree. C., 280
psig, GHSV = 1000, H.sub.2 :CO = 2.15 Wt. % O.sub.2 Chemi- Metals
on % sorption % CO Run 16-20 Mesh Rutile Air Treat .mu. mol O.sub.2
/g Conver- No. TiO.sub.2 in TiO.sub.2 .degree.C. (3 hr.) Catalyst
sion ______________________________________ 1 12 Co 53.sup.(1) 250
213 67 2 12 Co 100.sup.(2) 250 265 79 3 12 Co 56.sup.(3) 500 178 54
4 12 Co 100.sup.(2) 500 202 67 5 12 Co-3 Re 56.sup.(3) 500 399 81 6
12 Co-.5 Re 100.sup.(2) 500 285 82 7 12 Co-.1 Re 100.sup.(2) 500
145 67 8 12 Co-.5 Re 56.sup.(3) 500 343 85 3 Re 56.sup.(3) 500 149
<1 ______________________________________ .sup.(1)
Rutile:Anatase ratio 1.1:1. .sup.(2) Rutile:Anatase ratio >30:1.
.sup.(3) Rutile:Anatase ratio 1.3:1.
Reference is made to the intermediate curve plotted on FIG. 1 which
is representative of the data obtained from runs 1 and 2, of Table
I representing an unpromoted 12% Co catalyst the TiO.sub.2 support
having a rutile:anatase ratio of 1.1:1 (53% rutile content), and
another unpromoted 12% Co catalyst the support of which has a
rutile:anatase ratio >30:1. The rutile:anatase ratio, as
suggested, has been expressed in FIG. 1 as percentages for
convenience of expression, or to facilitate construction of the
graph. Both catalysts, represented on the graph by circled dots,
were calcined in air at 250.degree. C. Clearly the catalyst having
the high rutile TiO.sub.2 support is the superior catalyst
providing 79% CO conversion vis-a-vis 67% CO conversion obtained by
use of the catalyst having the lower rutile content TiO.sub.2
support. Referring now to the bottom curve on the figure there is
shown a plot representative of data obtained from runs 3 and 4,
viz., runs made with unpromoted cobalt catalysts similar to those
employed in runs 1 and 2, respectively, except that in these
instances both catalyst were calcined in air at 500.degree. C.
These catalysts are also represented on the graph by circled dots.
The unstabilized cobalt catalysts (as shown by a comparison of the
activities of the catalysts used in runs 3 and 4, vis-a-vis those
used in runs 1 and 2) both show a drop in activity due to the
calcination in air at 500.degree. C., which caused cobalt
agglomeration, or loss of cobalt dispersion. The cobalt catalyst
formed from a high rutile TiO.sub.2 support is clearly the superior
catalyst, the cobalt being more highly dispersed on the high rutile
support.
Reference is again made to FIG. 1, runs 5, 6, and 8 (represented by
black dots) being plotted as the top curve of the graphical data
presented. Run 5 was made with a 12% C0-3% Re--TiO.sub.2 (56%
rutile), run 6 with a 12% Co-0.5 Re--TiO.sub.2 (100% rutile), and
run 8 with a 12% Co-0.5% Re--TiO.sub.2 (56% rutile). These three
catalysts were calcined in air at 500.degree. C. These data clearly
show that the rhenium was adequate to stabilize the cobalt metal on
both of the catalysts against agglomeration, or loss of cobalt
dispersion. A 0.5% level of rhenium is sufficient to stabilize the
12% Co catalyst (Runs 6 and 8) against loss of cobalt metal
dispersion, it being noted that the rhenium promoted cobalt
catalyst (Runs 5, 6, or 8) is at least the equivalent of or
superior to the unpromoted cobalt wherein the cobalt is dispersed
on a 100% TiO.sub.2 rutile base.
Catalysts which contain at least 0.5% Re, as shown by the data,
provide consistently high activity after 500.degree. C. calcination
regardless of rutile content. In general, there is no significant
benefit obtained by adding a greater amount of rhenium. A 0.1 wt. %
rhenium level, however, is inadequate to fully protect a 12% Co
catalyst. Note that the rhenium promoted Co catalyst, 12% Co-0.1%
Re catalyst (Run 7), is mildly agglomerated after contact with air
at 500.degree. C.
These activity data can also be expressed as a pseudo first order
rate constant, k, represented by the equation ##EQU1## where
X=fraction CO conversion, P=reactor pressure, atm., and GHSV=space
velocity at ambient T and P, hr..sup.-1 A plot of k versus .mu. mol
O.sub.2 /g catalyst, determined by conventional dynamic O.sub.2
chemisorption, is shown by reference to FIG. 2. Note that for the
Co--Re catalysts the contribution of ReO.sub.2 chemisorption has
been subtracted out of the total chemisorption value to obtain a
chemisorption value for the cobalt component. The data fall on a
straight line correlation thus indicating that the activity of all
of these catalysts is a direct function of the cobalt dispersion.
Rhenium promoted catalysts show the highest activity because they
possess the highest cobalt dispersion. Such catalysts are also
quite stable and have strongly resisted agglomeration during the
500.degree. C. calcinations.
EXAMPLE 2
The surprisingly high activity of a Co--Re--TiO.sub.2 catalyst is
further demonstrated by a comparison of the 12% Co-0.5%
Re--TiO.sub.2 catalyst (100% rutile TiO.sub.2) of Example 1 with a
Ru--TiO.sub.2 catalyst, a known high activity catalyst.
A 60-150 mesh granulated 12% Co-0.5% Re--TiO.sub.2 (100% rutile)
catalyst was charged to a reactor, and contacted with a syngas
having an H.sub.2 :CO ratio of about 2 to 2.15 at 200.degree. C.,
280 psig, and GHSV=1000 for a period ranging up to 190 hours. For
comparative purposes, a similar run was subsequently made with a
80-150 mesh granulated 1% Ru--TiO.sub.2 (73% rutile; or 2.7:1
rutile:anatase) catalyst. Readings were taken at certain intervals,
and the product stream analyzed to determine the wt. % CO
conversion, and mol. % selectivity to CH.sub.4, CO.sub.2, C.sub.2 +
and the Schulz-Flory Alpha. Reference is made to Table II.
TABLE II ______________________________________ 200.degree. C., 280
psig, GHSV = 1000, H.sub.2 /CO = 2.0-2.15 12% Co--0.5%
Re--TiO.sub.2 60-150 mesh, 1% Ru--TiO.sub.2 Calcined 500.degree. C.
80-150 Mesh ______________________________________ Hours on Stream
15 75 190 4 162 CO Conversion, 98 86 78 45 22 wt. % Mol. %
Selectivity CH.sub.4 4.5 3.5 3.3 2.3 5.2 CO.sub.2 2.3 0.6 0.3 2.3
0.1 C.sub.2 + 93.2 95.9 96.4 95.4 94.7 Schulz-Flory Alpha -- 0.92
0.92 -- -- ______________________________________
As shown by the data, the 12% Co-0.5% Re--TiO.sub.2 catalyst is far
more active than the 1% Ru--TiO.sub.2 catalyst at 200.degree. C.,
and is capable of providing high CO conversion and high selectivity
to heavy hydrocarbons as indicated by the low CH.sub.4 +, CO.sub.2
by-product yields and high Schulz-Flory Alpha.
The results of the continuous 190 hour run presented in Table II
are graphically illustrated in FIG. 3. This high conversion run
produced a very heavy hydrocarbon product consisting principally of
linear paraffins with some linear olefins and branched components.
The Schulz-Flory Alpha was 0.92, indicative of about 80 wt. %
C.sub.10 + hydrocarbons in the product.
During the course of the continuous runs, gas hourly space velocity
was varied in order to obtain data at various levels of CO
conversion. The results comparing the Co--Re--TiO.sub.2 catalyst
with the Ru--TiO.sub.2 catalyst are graphically depicted in FIGS. 4
and 5. As shown in FIG. 4, the 12% Co-0.5% Re--TiO.sub.2 catalyst
is far more active than the 1% Ru--TiO.sub.2 catalyst at
200.degree. C., as determined by the higher conversion at a given
space velocity. The selectivity for CH.sub.4 and CO.sub.2 is quite
low for both of these catalysts as depicted by reference to FIG.
5.
EXAMPLE 3
Rhenium promoted cobalt catalysts are also very active for the
conversion of methanol to hydrocarbons. For purpose of
illustration, a series of runs were made with three cobalt
catalysts, viz., (1) 12% Co-2% ThO.sub.2 /TiO.sub.2, (2) 12% Co-2%
ThO.sub.2 -0.5% Re/TiO.sub.2, and (3) 12% Co-0.5 Re/TiO.sub.2,
formed by impregnation of 16-20 mesh TiO.sub.2 (56% rutile). Each
catalyst was charged to the reactor and air calcined at 500.degree.
C. In conducting the runs, methanol, with argon, was passed over
each of the catalysts at 230.degree. C., 400 psig, GHSV=500, and
CH.sub.3 OH/Ar=4 with the results obtained by reference to Table
III.
TABLE III ______________________________________ Methanol
Conversion 230.degree. C., 400 psig, GHSV = 500, CH.sub.3 OH/Ar = 4
(16-20 Mesh Catalysts, Calcined 500.degree. C.) 12% Co-- 12% Co--
2% ThO.sub.2 -- 12% Co-- 2% ThO.sub.2 0.5% Re 0.5% Re
______________________________________ CH.sub.3 OH Conversion 49
100 87 Carbon Product Distribution, Wt. % CO 6 2 2 CO.sub.2 14 28
22 CH.sub.4 6 14 9 C.sub.2 + 74 56 67
______________________________________
These data clearly show that the Co--Re--TiO.sub.2 and
Co--ThO.sub.2 --Re--TiO.sub.2 catalysts provide high levels of
conversion compared to the unpromoted Co--ThO.sub.2 --TiO.sub.2
catalyst, a preferred catalyst for this reaction, although
selectivities to C.sub.2 + hydrocarbons in each instance is debited
to some extent by a high CO.sub.2 make. This high water gas shift
activity with methanol is not observed with a syngas feed.
The following data show that the cobalt catalysts are activated for
syngas conversion by reducing the cobalt prior to use of the
catalyst for the conversion of syngas to hydrocarbons.
EXAMPLE 4
A series of runs were made at similar conditions with portions of a
Co--TiO.sub.2 catalyst (12% Co-0.5% Re/TiO.sub.2 (100% rutile)
after pretreatment of the different portions for three hours with
hydrogen at 200.degree. C., 235.degree. C., 300 .degree. C., and
450.degree. C., respectively. The runs were carried out by contact
of the catalysts, in different runs at 200.degree. C., 280 psig.
GHSV=1000 and H.sub.2 :CO=2.15, with a synthesis gas comprised of
an admixture of hydrogen and carbon monoxide. The results are given
in Table IV.
TABLE IV ______________________________________ 12% Co-0.5%
Re--Rutile, 60-150 Mesh, Calcined 500.degree. C. - 3 Hr.
200.degree. C., 280 psig, GHSV = 1000, H.sub.2 /CO = 2.15 Reduction
Temperature, .degree.C. CO Conversion
______________________________________ 200 0 235 8 300 98 450 99
______________________________________
The results show that the high temperature reduction is necessary
to activate the catalyst for conversion of syngas. Reduction of the
cobalt above about 250.degree. C., and preferably above about
300.degree. C. is necessary. Suitably, the reduction is carried out
at temperatures ranging from about 250.degree. C. to about
500.degree. C., and preferably from about 300.degree. C. to about
450.degree. C., with hydrogen or a hydrogen-containing gas.
It is apparent that various modifications and changes can be made
without departing the spirit and scope of the present
invention.
* * * * *